TW201841735A - Light-transmissive substrate for reflecting heat rays, and heat-ray-reflecting window - Google Patents

Abstract

Provided is a light-transmissive substrate for reflecting heat rays, the light-transmissive substrate having: a light-transmissive substrate; a hard coat layer disposed on one surface of the light-transmissive substrate; and a transparent electroconductive oxide layer containing a transparent electroconductive oxide, the transparent electroconductive oxide layer being disposed on the hard coat layer.

Description

Heat ray reflecting transparent substrate, heat ray reflecting window

The present invention relates to a heat ray reflecting transparent substrate and a heat ray reflecting window.

A heat ray-reflecting light-transmitting substrate having a layer having a heat ray reflection function on a light-transmitting substrate such as glass or resin is known. As a heat-ray-reflecting light-transmitting substrate, there has been previously studied a method for reflecting near-infrared rays and / or near-infrared rays to suppress near-infrared rays from entering indoors and / or cars, and to suppress temperature rise The heat-shielding heat rays reflect the light-transmitting substrate. In addition, in recent years, a heat-reflecting light-transmitting substrate having heat-cutting properties by reducing emissivity has been studied. For example, Patent Document 1 discloses a transparent substrate having a laminated substrate and a transparent substrate with a laminated film for the purpose of providing not only high heat shielding properties, high color rendering properties, but also excellent durability. A transparent substrate with a laminated film on which a laminated film of a transparent conductive layer and a nitrogen-containing light absorbing layer having a thickness of more than 10 nm is laminated. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Publication No. 2016-79051

[Problems to be Solved by the Present Invention] However, in terms of functions, the heat-ray-reflecting light-transmitting base material is used as a light-transmitting base material for a lighting portion of a window or the like, or attached to a window or the like. Since the lighting unit is used on a light-transmitting substrate, there are many opportunities for contact with human hands and / or objects. For this reason, even when a person's hand, an object, or the like moves while generating friction while applying pressure to the surface of a light-transmitting substrate that reflects heat rays, there is a requirement to prevent the formation of heat rays. Functional layers such as transparent conductive layers that reflect the light-transmitting substrate are exfoliated, imperfect, and the like, resulting in reduced functionality and impaired appearance. That is, there is a need for a heat-ray-reflecting light-transmitting substrate having excellent scratch resistance. However, the transparent substrate with a laminated film disclosed in Patent Document 1 has not been studied sufficiently against the abrasion resistance. Therefore, in view of the above-mentioned problems of the prior art, in one aspect of the present invention, it is an object of the present invention to provide a heat-ray-reflecting light-transmitting substrate having excellent scratch resistance. [Means for Solving the Problems] In order to solve the above problems, in one aspect of the present invention, a heat-ray-reflecting light-transmitting substrate is provided, including: a light-transmitting substrate; and a surface hardened layer disposed on the light-transmitting substrate. On one surface of the material; and a transparent conductive oxide layer disposed on the surface hardened layer and containing a transparent conductive oxide. [Effects of the Present Invention] According to an aspect of the present invention, it is possible to provide a heat-ray-reflecting light-transmitting substrate having excellent scratch resistance.

Hereinafter, one embodiment of the present disclosure (hereinafter referred to as "this embodiment") will be described in detail, but this embodiment is not limited to this. [Heat Ray Reflective and Translucent Substrate] A configuration example of the heat ray reflecting and translucent substrate according to this embodiment will be described below. The heat-ray-reflecting light-transmitting substrate according to this embodiment includes a light-transmitting substrate, a hard coat layer disposed on one surface of the light-transmitting substrate, and a transparent conductive material disposed on the surface-hardening layer. A transparent conductive oxide layer of an oxide. The inventors of the present invention have conducted intensive studies in order to reduce the emissivity and make the heat ray reflecting and translucent base material having thermal insulation properties a heat ray reflecting and translucent base material having excellent scratch resistance. As a result, it was first found that a transparent conductive oxide layer containing a transparent conductive oxide can be a heat-ray-reflecting light-transmitting substrate having a thermal insulation property. The reason for this is considered to be that the far-infrared rays can be reflected by using a carrier included in the transparent conductive oxide contained in the transparent conductive oxide layer. However, in the case where only the transparent conductive oxide layer is disposed on the light-transmitting substrate, for example, when a hand and / or an object is moved while being rubbed while the transparent conductive oxide layer is pressed, there is a problem. The transparent conductive oxide layer is deformed, which may cause peeling, flaws, and the like of the transparent conductive oxide layer. When flaws, peeling, and the like occur on the transparent conductive oxide layer, the function of the transparent conductive oxide layer may be reduced and the appearance may be damaged. Therefore, it has been found that by disposing a surface-hardened layer on a light-transmitting substrate, even when the transparent conductive oxide layer is pressed or rubbed, the deformation of the transparent conductive oxide layer can be reduced, so that the The present invention has been accomplished by suppressing the occurrence of flaws, peeling, and the like, that is, improving the abrasion resistance. Here, FIG. 1 shows a configuration example of a heat ray reflecting translucent substrate according to this embodiment. FIG. 1 is a schematic cross-sectional view of a surface parallel to the lamination direction of the light-transmitting substrate, the surface-hardened layer, and the transparent conductive oxide layer of the heat-ray-reflecting light-transmitting substrate according to the present embodiment. As shown in FIG. 1, the heat-ray-reflecting light-transmitting substrate 10 according to this embodiment may have transparent conductive oxidation disposed on the surface-hardened layer 12 and the surface-hardened layer 12 on one surface of the light-transmitting substrate 11. The object layer 13 has a laminated structure. Each layer is described below. As the light-transmitting substrate 11, various light-transmitting substrates capable of transmitting (transmitting) visible light can be preferably used. As the light-transmitting substrate 11, a light-transmitting substrate having a visible light transmittance of 10% or more can be preferably used. In addition, in this specification, the visible light transmittance is measured in accordance with JIS A5759-2008 (building window glass film). As the translucent base material 11, a glass plate, a translucent resin base material, etc. can be used preferably. In the heat-ray-reflecting light-transmitting substrate according to the present embodiment, by providing a surface hardened layer, deformation of the transparent conductive oxide layer can be suppressed, thereby improving scratch resistance. In addition, when the light-transmitting substrate is particularly easily deformed, such as a light-transmitting resin substrate, the above-mentioned effects are exhibited. Therefore, the light-transmitting substrate of the heat-ray-reflecting light-transmitting substrate of the present embodiment is preferably a light-transmitting resin substrate. As the material of the light-transmitting resin substrate, as described above, any material that can transmit visible light can be preferably used. However, there are cases where heat treatment or the like is performed when each layer is formed on the light-transmitting substrate 11. Therefore, a resin having heat resistance can be preferably used. As the resin material constituting the light-transmitting resin substrate, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), and polyether One or more selected from carbonate (PC) and the like. The heat-ray-reflecting light-transmitting substrate according to the present embodiment can be used as a light-transmitting substrate for a light collecting portion of a window, for example, by being embedded in a window frame or the like, or by being attached to a window or the like It is used as a light-transmitting substrate on a light-emitting portion. For this purpose, the thickness and / or material of the light-transmitting substrate 11 can be selected according to the application and the like. The thickness of the translucent substrate 11 may be, for example, 10 μm or more and 10 mm or less. For example, when the heat-ray-reflecting translucent substrate of the present embodiment is used as a translucent substrate of a light collecting portion such as a window, it is preferable to select the thickness and / or material of the translucent substrate 11. So that it has sufficient strength. In addition, when the heat-ray-reflecting transparent substrate of the present embodiment is used by being bonded to a light-transmitting substrate of a lighting portion such as a window, in order to improve the productivity of the heat-ray reflecting substrate, and to facilitate It is preferable to attach the light-transmitting base material such as a window, and the thickness and / or material of the light-transmitting base material 11 to be flexible. In the case of a flexible light-transmitting substrate, a light-transmitting resin substrate is preferably used as the light-transmitting substrate. When a light-transmitting resin substrate is used as the light-transmitting substrate having flexibility, the thickness is preferably in a range of about 10 μm or more and about 300 μm or less. In addition, although the translucent base material 11 may be comprised by 1 translucent base material, for example, you may combine and use 2 or more translucent base materials, and use them together. Even when two or more light-transmitting substrates are bonded and used in combination, the total thickness preferably satisfies the preferable thickness range of the above-mentioned light-transmitting substrate, for example. The surface hardened layer 12 supports the transparent conductive oxide layer 13 and can suppress the deformation of the transparent conductive oxide layer 13 when it is pressed or the like. The surface hardened layer 12 can be formed using a resin, for example, and can be a resin surface hardened layer. The material of the surface hardened layer is not particularly limited. For example, one or more resins selected from acrylic resins, silicone resins, and urethane resins can be preferably used. In addition, by including inorganic particles in the surface-hardened layer, the adhesion between the surface-hardened layer and the transparent conductive layer can be improved. The material of the inorganic particles is not particularly limited, but for example, one or more inorganic particles selected from silica, alumina, and zirconia can be preferably used. The surface hardened layer 12 can be formed, for example, by applying a resin to one surface of the light-transmitting base material 11 and curing it. The thickness of the surface hardened layer 12 is not particularly limited, and can be arbitrarily selected according to the material of the surface hardened layer 12, the required transmittance of visible light, the degree of scratch resistance, and the like. The thickness of the surface-hardened layer 12 is, for example, preferably 0.5 μm or more and 10 μm or less, and more preferably 0.7 μm or more and 5 μm or less. The reason is that by making the thickness of the surface-hardened layer 12 0.5 μm or more, a surface-hardened layer having sufficient strength can be used, and in particular, deformation of the transparent conductive oxide layer 13 can be suppressed. Furthermore, by making the thickness of the surface-hardened layer 12 to 10 μm or less, it is possible to suppress internal stress caused by shrinkage of the surface-hardened layer. The transparent conductive oxide layer 13 is a layer containing a transparent conductive oxide, and may be a layer made of a transparent conductive oxide. According to the study by the inventor of the present invention, it is found that carriers contained in the transparent conductive oxide can reflect far infrared rays. For this reason, by providing a transparent conductive oxide layer, the heat-ray-reflecting and translucent base material of this embodiment can be a heat-ray-reflecting and translucent base material with superior thermal insulation. The transparent conductive oxide contained in the transparent conductive oxide layer is not particularly limited, and any transparent conductive oxide can be used as long as it can reflect far infrared rays. However, as described above, since far-infrared rays are reflected by a carrier, the transparent conductive oxide preferably contains, for example, one or more selected from indium oxide, tin oxide, and zinc oxide. Indium is doped with one or more selected from tin, titanium, tungsten, molybdenum, zinc, and hydrogen, and the tin oxide is doped with one or more selected from antimony, indium, tantalum, chlorine, and fluorine. The zinc oxide is doped with at least one selected from indium, aluminum, tin, gallium, fluorine, and boron. The transparent conductive oxide is preferably doped with one or more kinds of indium oxide selected from tin, titanium, tungsten, molybdenum, zinc, and hydrogen, and more preferably doped with tin and zinc. More than one indium oxide. The thickness of the transparent conductive oxide layer is not particularly limited, and can be arbitrarily selected according to the required thermal insulation properties and the like. For example, the thickness of the transparent conductive oxide layer is preferably 30 nm to 500 nm, and more preferably 35 nm to 400 nm. The reason for this is that, by setting the thickness of the transparent conductive oxide layer to 30 nm or more, far-infrared rays can be reflected in particular, thereby improving the thermal insulation performance. It is also because by setting the thickness of the transparent conductive oxide layer to 500 nm or less, the visible light transmittance can be maintained sufficiently high. The method for forming the transparent conductive oxide layer is not particularly limited, but for example, a dry method based on any one or more selected from a sputtering method, a vacuum evaporation method, a CVD method, an electron beam evaporation method, or the like can be preferably used. Processed film formation method. In addition, it is preferable to perform heat treatment after film formation to improve crystallinity in advance. The heat-ray-reflecting light-transmitting substrate of the present embodiment is not limited to the light-transmitting substrate, the surface-hardened layer, and the transparent conductive oxide layer described above, and may have any layer. For example, an underlayer such as a light adjustment layer, a gas barrier layer, or an adhesion improvement layer may be provided between the surface hardened layer and the transparent conductive oxide layer. The light adjustment layer can improve the color and / or transparency, the gas barrier layer can improve the crystallization speed of the transparent conductive oxide, and the adhesion improvement layer can achieve anti-layer peeling and crack resistance. The improvement in durability is not particularly limited to the specific structure of the underlayer, but examples of the adhesion improvement layer and / or the gas barrier layer include a layer containing alumina (Al ₂ O ₃ ). Examples of the light adjustment layer include a layer containing zirconia (ZrO ₂ ), a layer containing hollow particles, and the like. For example, with respect to the heat-ray-reflecting translucent substrate according to this embodiment, as shown in FIG. 2, the heat-ray-reflecting translucent substrate 20 may be hardened on the surface of the light-transmitting substrate 11 and provided with a surface hardening. The layer 12 and the transparent conductive oxide layer 13 have an adhesive layer 21 on the other surface 11 b on the opposite side of the surface 11 a. As described above, the heat-ray-reflecting light-transmitting substrate of the present embodiment can also be used by being attached to a light-transmitting substrate of a lighting unit such as a window. For this reason, by providing the adhesive layer 21 as described above, it is possible to easily adhere to a light-transmitting substrate of a lighting portion such as a window. The material of the adhesive layer is not particularly limited, but a material having a high visible light transmittance is preferably used. As the material of the adhesive layer, for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, or the like can be used. Among them, the propylene-based adhesive mainly composed of a propylene-based polymer has excellent optical transparency, has appropriate wettability, agglutination, and adhesion, and is also more weather-resistant and heat-resistant. Since it is excellent, it is preferable as a material of an adhesive layer. The adhesive layer preferably has a high visible light transmittance and a small ultraviolet transmittance. By making the ultraviolet transmittance of the adhesive layer small, deterioration of the light-transmitting substrate, the surface-hardened layer, and the transparent conductive oxide layer caused by ultraviolet rays such as sunlight can be suppressed. From the viewpoint of making the ultraviolet transmittance of the adhesive layer small, the adhesive layer may further contain an ultraviolet absorbent. In addition, by using a translucent substrate or the like containing an ultraviolet absorber, deterioration of the transparent conductive oxide layer due to ultraviolet rays from the outside can also be suppressed. The exposed surface of the adhesive layer is preferably temporarily covered with a release paper in order to prevent the exposed surface from being contaminated or the like until it is provided to the heat-ray-reflecting transparent substrate. Accordingly, it is possible to prevent contamination due to contact with the outside of the exposed surface of the adhesive layer in a normal operation state. In addition, when the heat-ray-reflecting translucent base material of this embodiment is embedded in a window frame or the like and used as a translucent base material of a lighting part such as a window, it is not necessary to attach it to other light-transmitting materials. It is preferable not to have an adhesive layer on a flexible substrate. In addition, as for the heat ray reflection translucent base material of this embodiment, as shown in FIG. 3, the heat ray reflection translucent base material 30 may further have a surface protective layer on the transparent conductive oxide layer 13. 31. It should be noted that the heat-ray-reflecting translucent substrate 30 may include a surface-hardened layer 12 and a translucent substrate 11 under the transparent conductive oxide layer 13 as shown in FIG. 3. By providing the surface protection layer 31, the transparent conductive oxide layer 13 can be prevented from directly contacting a person's hand or the like, and especially the scratch resistance can be improved. The thickness of the surface protective layer is preferably 5 nm or more and 1 μm or less, and more preferably 5 nm or more and 500 nm or less. The reason is that by setting the thickness of the surface protective layer to 5 nm or more, the transparent conductive oxide layer 13 can be sufficiently protected, and particularly the scratch resistance can be improved. In addition, even if the thickness of the surface protective layer is increased to more than 1 μm, there is no significant difference in effect. On the other hand, there is a possibility that the absorption of far infrared rays may cause an increase in emissivity, so it is preferably 1 μm or less. As the material of the surface protective layer 31, it is preferable that the visible light transmittance is high, and mechanical strength and chemical strength are both excellent. From a viewpoint of improving the scratch prevention and / or chemical protection effect with respect to a transparent conductive oxide layer, an organic material and / or an inorganic material are preferable. As the organic material, for example, a fluorine-based, acrylic-based, polyurethane-based, ester-based, epoxy-based, silicon-based, olefin-based active light-curing or thermosetting organic material is preferably used, and / or organic Organic and inorganic hybrid materials with chemical bonding of components and inorganic components. Examples of the inorganic material include transparent oxides containing at least one selected from silicon, aluminum, zinc, titanium, zirconium, and tin as a main component, and DLC (diamond-like carbon). )Wait. When an organic material is used as the surface protective layer 31, a cross-linked structure is preferably introduced into the organic material. By forming the crosslinked structure, the mechanical strength and chemical strength of the surface protective layer can be improved, and the protective function against the transparent conductive oxide layer and the like can be improved. Among them, it is preferable to introduce a crosslinked structure derived from an ester compound having an acidic group and a polymerizable functional group in the same molecule. Examples of the ester compound having an acidic group and a polymerizable functional group in the same molecule include polyvalent acids such as phosphoric acid, sulfuric acid, oxalic acid, succinic acid, phthalic acid, fumaric acid, and maleic acid, and the molecule An ester of a compound having a polymerizable functional group such as an ethylene unsaturated group, a silanol group, and an epoxy group, and a hydroxyl group. In addition, although this ester compound may be a polyvalent ester, such as a diester and a triester, it is preferable that at least 1 acidic group of a polyvalent acid is not esterified. When the surface protective layer 31 has a crosslinked structure derived from the above-mentioned ester compound, the mechanical strength and chemical strength of the surface protective layer can be improved, and the adhesion between the surface protective layer 31 and the transparent conductive oxide layer 13 can be improved. In particular, the durability of the transparent conductive oxide layer can be improved. Among the above-mentioned ester compounds, the adhesion between the ester compound of phosphoric acid and an organic acid having a polymerizable functional group (phosphate ester compound) and the transparent conductive oxide layer is excellent. In particular, the adhesion between the surface protective layer having a crosslinked structure derived from a phosphate compound and the transparent conductive oxide layer is particularly good. From the viewpoint of improving the mechanical strength and chemical strength of the surface protective layer 31, the ester compound preferably contains (meth) acryloyl as a polymerizable functional group. In addition, from the viewpoint of easy introduction of a cross-linked structure, the above-mentioned ester compound may have a plurality of polymerizable functional groups in its molecule. As the ester compound, for example, a phosphoric acid monoester compound or a phosphoric acid diester compound represented by the following formula (1) can be preferably used. In addition, a phosphoric acid monoester and a phosphoric acid diester may be used simultaneously. [Chemized 1] Wherein, X represents a hydrogen atom or a methyl group, (Y) represents -OCO (CH _{2) 5} - group. n is 0 or 1, and p is 1 or 2. The content of the structure derived from the ester compound in the surface protective layer 31 is preferably 1% by mass or more and 20% by mass or less, preferably 1.5% by mass or more and 17.5% by mass or less, more preferably 2% by mass or more and 15% by mass % Or less, particularly preferably 2.5% by mass or more and 12.5% by mass or less. When the content of the structure derived from the ester compound is too small, the effect of improving strength and / or adhesion may not be sufficiently obtained. On the other hand, if the content of the structure derived from the ester compound is too large, a decrease in the hardening rate when forming the surface protective layer results in a decrease in hardness, and / or a decrease in the sliding properties of the surface of the surface protective layer results in a decrease in scratch resistance. Case. Regarding the content of the structure derived from the ester compound in the surface protective layer, when the surface protective layer is formed, the content of the ester compound in the composition can be adjusted so that it is within a desired range. The method for forming the surface protective layer 31 is not particularly limited. The surface protective layer is preferably formed, for example, by dissolving an organic material or a curable monomer and / or oligomer of the organic material in a solvent together with the ester compound to prepare a solution, and The solution is applied on the transparent conductive oxide layer 13, and then the solvent is dried and then cured by a method of irradiating with ultraviolet rays and / or electron beams and / or applying (applying) thermal energy to harden it. form. When an inorganic material is used as the material of the surface protective layer 31, for example, any one or more dry methods selected from a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method can be used. The process proceeds to film formation. It should be noted that, as a material of the surface protective layer 31, in addition to the above-mentioned organic materials and / or inorganic materials, a coupling agent such as a silane coupling agent (titanium coupling agent), or a titanium coupling agent (titanium coupling agent) may be included. Additives such as crosslinking agents, leveling agents, UV absorbers, oxidation inhibitors, heat stabilizers, lubricants, plasticizers, colorants, flame retardants, and antistatic agents. In addition, the surface protective layer 31 may be composed of a plurality of layers having different materials by laminating an inorganic material and an organic material. The characteristics required for the heat ray reflecting translucent substrate of the present embodiment are not particularly limited, but the emissivity measured from one side of the transparent conductive oxide layer is preferably 0.60 or less, preferably 0.50 or less, and more preferably 0.40. the following. The reason for this is that it is preferable that the emissivity is 0.60 or less, because it can be a heat ray reflecting translucent substrate having sufficient thermal insulation properties. It should be noted that there is no particular limitation on the lower limit of the emissivity, but a smaller value is preferred, and it may be greater than 0, for example. As described above, the heat-ray-reflecting light-transmitting substrate of the present embodiment includes a light-transmitting substrate, a surface-hardened layer, and a transparent conductive oxide layer. In addition, the emissivity measured from one side of the transparent conductive oxide layer means that one of the transparent conductive oxide layers among the three layers described above is reflected on the surface of the light-transmitting substrate from heat rays. The emissivity measured by irradiating infrared rays or the like to the transparent conductive oxide layer on the side surface. [Heat ray reflection window] Next, a configuration example of the heat ray reflection window of the present embodiment will be described. As shown in FIG. 4, the heat ray reflection window 40 according to the present embodiment may include a window translucent substrate 41 and the above-mentioned heat ray reflection transmissive property arranged on one surface 41 a of the window translucent substrate 41. Substrate 42. The light-transmissive substrate 41 for windows is, for example, a light-transmissive substrate disposed on a lighting portion of a window or the like, and a glass plate and / or a light-transmissive resin substrate can be used, for example. The heat-reflecting light-transmitting base material 42 may be disposed on one surface of the light-transmitting base material 41 for windows. The method of fixing the heat-ray-reflecting light-transmitting substrate 42 to the window-light-transmitting substrate 41 is not particularly limited. The surface 42b facing the material 41 is fixed on the side of the surface 42b based on the adhesive layer or the like described with reference to FIG. 2. When fixing the heat-ray-reflecting translucent base material 42 to the window translucent base material 41, it is preferable to fix it so that a transparent conductive oxide layer is located indoors and / or the inside of a car. That is, it is preferable that the heat ray reflecting translucent base material 42 is located in the room and / or the vehicle with a transparent conductive oxide layer than the light transmissive base material having the heat ray reflecting translucent base material 42. The inner way is fixed. Generally, the heat-ray-reflecting translucent substrate 42 is disposed on the indoor side of the window-transparent substrate 41. For this reason, in the example shown in FIG. 4, it is preferable that a transparent conductive oxide layer is located on the opposite side of the one surface 42 b of the heat ray reflecting translucent substrate 42 opposite to the window translucent substrate 41. The other surface is fixed on the side of 42a. The reason is that the transparent conductive oxide layer has a function of reflecting far-infrared rays. Therefore, by arranging the transparent conductive oxide layer toward a room or the like, it is possible to suppress radiation of far-infrared rays generated in the room or the like to the outside. It can be seen that the heat ray reflection window includes the heat ray reflection translucent base material. For this reason, the far-infrared rays can be reflected to have a heat-insulating function. In addition, it can be a heat ray reflection window with excellent abrasion resistance. [Examples] Hereinafter, description will be made with reference to specific examples, but the present invention is not limited to these examples. (1) Visible light transmittance Visible light transmittance was determined using a spectrophotometer (manufactured by Hitachi High Tech, product name "U-4100") in accordance with JIS A5759-2008 (building window glass film). (2) Emissivity In terms of emissivity, a Fourier-transformed infrared spectroscopy (FT-IR) device (manufactured by "Varian") with an angle-variable reflection accessory is used to irradiate the wavelength from the surface protective layer side The specular reflectance in the case of infrared rays in a range of 5 μm or more and 25 μm or less was measured and measured in accordance with JIS R3106-2008 (Test method for transmittance, reflectance, emissivity, and solar radiant heat acquisition rate of sheet glass). ). (3) Abrasion resistance The surface of the light-transmitting substrate side of the heat-reflecting light-transmitting substrate cut to 15 cm × 5 cm was bonded to a glass of 1.5 mm with an adhesive layer having a thickness of 25 μm. The composition was used as a sample (sample). Using a 10-pen tester, while applying a load of 1 kg through steel wool (Bonstar # 0000), the heat rays fixed on the glass reflected the exposed surface of the transparent substrate Ten back and forth rubs were performed over a length of 10 cm. It should be noted that the exposed surfaces of the heat-ray-reflecting light-transmitting substrate are surface protection layers in Examples 1 to 9, Example 11 to Example 13, Comparative Example 1, and Comparative Example 2. The surface of is a surface of the transparent conductive oxide layer in Example 10. The presence or absence of flaws and / or peeling of the transparent conductive oxide layer of the sample after the test was visually evaluated according to the following evaluation criteria. 〇: No blemishes and / or peeling was observed on the transparent conductive oxide layer △: No blemishes and / or peeling was confirmed on a part of the transparent conductive oxide layer ×: Confirmed on the transparent conductive oxide layer Defects and / or peeling [Example 1] A heat-ray-reflecting light-transmitting substrate having a structure shown in Table 1 was produced and evaluated. As shown in Table 1, a heat-ray-reflecting light-transmitting substrate having a light-transmitting substrate, a surface hardened layer, a transparent conductive oxide layer, and a surface protective layer was produced. As the light-transmitting substrate, a polyethylene terephthalate (PET) film (manufactured by Mitsubishi Resin Co., Ltd., trade name: T602E50) was used with a thickness of 50 μm. The resin solution was applied on one surface of the light-transmitting substrate by spin coating and dried, and then irradiated with ultraviolet (UV) (300 mJ) under a nitrogen atmosphere (ambient gas). / cm ² ), and a surface-hardened layer having a thickness shown in Table 1 was formed. The resin solution is a photopolymerization initiator in a UV-curable urethane acrylate-based hard coat resin solution ("DIC Corporation", trade name: ENS1068). (Manufactured by "BASF Corporation", trade name: Irgacure 184) was produced by mixing so that the resin equivalent became 3 wt%. An ITO film (Indium Tin Oxide film, that is, an indium tin oxide film) was formed on the surface hardened layer as a transparent conductive oxide layer. Specifically, the content of SnO ₂ with respect to the total amount of IN ₂ O ₃ and SnO ₂ to 10 wt% of a composite oxide target, and by DC magnetron sputtering (magnetron sputtering) method, Table 1 were The film was formed into a film having the indicated thickness and then subjected to a heat treatment at 150 ° C. for 30 minutes. It should be noted that the sputtering gas used a mixed gas of argon and a small amount of oxygen, and was formed into a film under a process pressure of 0.2 Pa. A film of a surface protective layer was formed on the transparent conductive oxide layer. Specifically, a photopolymerization initiator (manufactured by BASF Corporation, trade name: Irgacure127) was prepared in a propylene-based surface-hardening resin solution (manufactured by "JSR Corporation", trade name: OPSTAR Z7535) to a resin equivalent of 3 The mixed solution was mixed in a wt% manner. Then, this mixed solution was applied to the transparent conductive oxide layer by a spin coating method so that the thickness after drying became the thickness shown in Table 1. After drying, it was hardened by irradiating UV (300 mJ / cm ² ) under a nitrogen atmosphere. The obtained heat-ray-reflecting light-transmitting substrate was evaluated as described above. The results are shown in Table 1. [Examples 2 and 3] A heat-ray-reflecting light-transmitting substrate was produced and evaluated in the same manner as in Example 1 except that the transparent conductive oxide layer was made to have the thickness shown in Table 1. The results are shown in Table 1. [Example 4] A heat-ray-reflecting light-transmitting substrate was produced and evaluated in the same manner as in Example 1 except that the surface protective layer was formed in the thickness shown in Table 1. The results are shown in Table 1. [Example 5] A heat-ray-reflecting light-transmitting substrate was produced and evaluated in the same manner as in Example 1 except that the surface protective layer had the following configuration. The results are shown in Table 1. An oxide film (described as "SXO" in Table 1) containing Si and Zr was formed as a surface protective layer on the transparent conductive oxide layer. Specifically, an alloy target having a Zr content of 30% by weight relative to the total amount of metal Si and Zr was used, and a film was formed in a thickness shown in Table 1 by a DC magnetron sputtering method. The sputtering gas was a mixed gas of argon / oxygen = 85/15 (volume ratio), and film formation was performed under a processing gas pressure of 0.2 Pa. The evaluation results are shown in Table 1. [Example 6] A heat-ray-reflecting transparent substrate was produced and evaluated in the same manner as in Example 1 except that the surface protective layer was formed into a film having the thickness shown in Table 1. The results are shown in Table 1. [Example 7] As a transparent conductive oxide layer, instead of an ITO film, an IZO film (Indium Zinc Oxide film, that is, an indium zinc oxide film) was formed to a thickness of 400 nm. Except for this point, In Example 1, a heat-ray-reflecting light-transmitting substrate was produced in the same manner and evaluated. The results are shown in Table 1. For the IZO film, a composite oxide target having a content of ZnO of 10 wt% relative to the total amount of In ₂ O ₃ and ZnO was used, and a thickness of 400 nm was formed by a DC magnetron sputtering method. membrane. It should be noted that the sputtering gas used a mixed gas of argon and a small amount of oxygen, and was formed under a processing pressure of 0.2 Pa. The evaluation results are shown in Table 1. [Example 8] A heat-ray-reflecting light-transmitting substrate was produced and evaluated in the same manner as in Example 3 except that the surface-hardened layer was formed into a film having the thickness shown in Table 1. The results are shown in Table 1. [Example 9] A heat-ray-reflecting light-transmitting substrate was produced and evaluated in the same manner as in Example 1 except that the surface hardened layer was formed into a film having the thickness shown in Table 1. The results are shown in Table 1. [Example 10] As a light-transmitting substrate, a blue plate glass (manufactured by "Matsulang Glass Co., Ltd.") having a thickness of 3 mm was used, and a surface protective layer was not provided. Except for these, it was the same as Example 1 A heat-ray-reflecting light-transmitting substrate was produced and evaluated. The results are shown in Table 1. [Example 11] A heat-ray-reflecting translucent substrate was produced and evaluated in the same manner as in Example 1 except that the transparent conductive oxide layer was formed into a film having the thickness shown in Table 1. The results are shown in Table 1. [Example 12] A heat-ray-reflecting light-transmitting substrate was produced and evaluated in the same manner as in Example 1 except that the surface protective layer was formed into a film having the thickness shown in Table 1. The results are shown in Table 1. [Example 13] A heat-ray-reflecting light-transmitting base material was produced in the same manner as in Example 1 except that the underlying film was formed between the surface hardened layer and the transparent conductive oxide layer. Evaluation. On the surface hardened layer, an adhesion-improving layer, that is, an Al oxide film, that is, an aluminum oxide film (described as "Al ₂ O ₃ " in Table 1) was formed as a bottom layer. Specifically, a metal Al target was used on the surface-hardened layer, and an underlayer having a thickness shown in Table 1 was formed by a DC magnetron sputtering method. The sputtering gas was a mixed gas of argon / oxygen = 85/15 (volume ratio), and film formation was performed under a processing gas pressure of 0.2 Pa. After the underlayer was formed, a transparent conductive oxide layer and a surface protective layer were formed on the underlayer in the same manner as in Example 1. Thus, a heat ray reflecting transparent substrate was obtained. The evaluation results are shown in Table 1. [Comparative Example 1] A heat-ray-reflecting light-transmitting substrate was produced in the same manner as in Example 1 except that a surface hardened layer was not provided, and was evaluated. The results are shown in Table 1. [Comparative Example 2] A heat-ray-reflecting transparent substrate was produced and evaluated in the same manner as in Example 1 except that a SiO ₂ film was formed instead of the transparent conductive oxide layer. The results are shown in Table 1. For the SiO ₂ layer, a metal Si target was used, and a film was formed with a thickness of 80 nm by a DC magnetron sputtering method. The sputtering gas was a mixed gas of argon / oxygen = 85/15 (volume ratio), and film formation was performed under a processing pressure of 0.2 Pa. The evaluation results are shown in Table 1. [Table 1] Based on the results shown in Table 1, when Examples 1 to 13 and Comparative Example 1 were compared, it was confirmed that by providing a surface hardened layer, a heat ray-reflecting light-transmitting substrate having excellent scratch resistance can be obtained. The reason is considered to be that the provision of the surface hardened layer can suppress deformation even when the transparent conductive oxide layer is pressed, and can suppress the occurrence of flaws, peeling, and cracks caused by friction. In addition, by comparing Examples 1 to 13 and Comparative Example 2 without a transparent conductive oxide layer, it was also confirmed that in Examples 1 to 13, compared with Comparative Example 2, the radiation The rate is greatly reduced, that is, by providing a transparent conductive oxide layer, thermal insulation properties can be exhibited. Although the heat ray reflection translucent base material and the heat ray reflection window have been described based on the embodiments and examples, the present invention is not limited to the above embodiments and examples. Various modifications and changes can be made within the scope of the gist of the present invention described in the patent application scope. This application claims priority based on Japanese Patent Application No. 2017-073174 filed with the Japanese Patent Office on March 31, 2017 and Japanese Patent Application No. 2018-049516 filed with the Japanese Patent Office on March 16, 2018, The contents of -073174 and Japanese Patent Application No. 2018-049516 are all incorporated in this international application.

10, 20, 30, 42‧‧‧ heat ray reflective translucent substrate

11‧‧‧ Transparent substrate

12‧‧‧ surface hardened layer

13‧‧‧ transparent conductive oxide layer

21‧‧‧Adhesive layer

31‧‧‧ surface protection layer

40‧‧‧ heat ray reflection window

41‧‧‧Transparent substrate for window

[FIG. 1] A cross-sectional view of a heat-ray-reflecting light-transmitting substrate according to a configuration example of an embodiment of the present invention. [FIG. 2] A cross-sectional view of a heat ray reflecting transparent substrate according to another configuration example of the embodiment of the present invention. [Fig. 3] A cross-sectional view of a heat ray reflecting transparent substrate according to another configuration example of the embodiment of the present invention. [FIG. 4] A cross-sectional view of a heat ray reflection window according to a configuration example of an embodiment of the present invention.

Claims (9)

A heat ray reflecting translucent substrate, comprising: a translucent substrate; a surface hardened layer disposed on one surface of the translucent substrate; a transparent conductive oxide layer disposed on the surface hardened layer, And contains transparent conductive oxide. The heat-ray-reflecting light-transmitting substrate according to claim 1, wherein the transparent conductive oxide layer contains indium oxide doped with one or more kinds selected from tin, titanium, tungsten, molybdenum, zinc, and hydrogen, Selected by doping one or more tin oxides selected from antimony, indium, tantalum, chlorine, and fluorine, and by doping one or more zinc oxides selected from indium, aluminum, tin, gallium, fluorine, and boron. Or more of them as the transparent conductive oxide. The heat-ray-reflecting translucent substrate according to claim 1 or 2, wherein the thickness of the transparent conductive oxide layer is 30 nm or more and 500 nm or less. The heat-ray-reflective translucent substrate according to any one of claims 1 to 3, wherein the thickness of the surface hardened layer is 0.5 μm or more and 10 μm or less. The heat-ray-reflective translucent substrate according to any one of claims 1 to 4, further comprising a surface protective layer on the transparent conductive oxide layer. The heat-ray-reflecting translucent substrate according to claim 5, wherein the thickness of the surface protective layer is 5 nm or more and 1 μm or less. The heat-ray-reflecting translucent substrate according to any one of claims 1 to 6, wherein an adhesive layer is provided on a surface of the translucent substrate opposite to the one surface. The heat-ray-reflecting translucent substrate according to any one of claims 1 to 7, wherein the emissivity measured from one side of the transparent conductive oxide layer is 0.60 or less. A heat ray reflection window comprising: a light-transmitting substrate for a window; and the heat-ray-reflecting light-transmitting substrate according to any one of claims 1 to 8 disposed on one surface of the light-transmitting substrate for a window. material.